Generation and transport of charge carriers in poly(phenyl‐phenylenevinylene) and poly(3‐dodecylthiophene) have been investigated by means of dc and transient photoconductivity. Geminate pairs are formed by disorder assisted partial dissociation of singlet excitons of chain segments followed by temperature and field assisted dissociation in accord with 1D Onsager theory. In PDT secondary hole injection from an AL- anode is responsible for quantum yields > 1. It is initiated by O2ions accumulated at the interface.